In Situ Biorestoration as a Ground Water Remediation Technique

In situ biorestoration, where applicable, is indicated as a potentially very cost-effective and environmentally acceptable remediation technology. Many contaminants in solution in ground water as well as vapors in the unsaturated zone can be completely degraded or transformed into new compounds by naturally occurring indigenous microbial populations. Undoubtedly, thousands of contamination events are remediated naturally before the contamination reaches a point of detection. The need is for methodology to determine when natural biorestoration is occurring, the stage the restoration process is in, whether enhancement of the process is possible or desirable, and what will happen if natural processes are allowed to run their course.
In addition to the nature of the contaminant, several environmental factors are known to influence the capacity of indigenous microbial populations to degrade contaminants. These factors include dissolved oxygen, pH, temperature, oxidation-reduction potential, availability of mineral nutrients, salinity, soil moisture, the concentration of specific pollutants, and the nutritional quality of dissolved organic carbon in the ground water.
Most enhanced in situ bioreclamation techniques available today are variations of hydrocarbon degradation procedures pioneered and patented by Raymond and coworkers at Suntech during the period 1974 to 1978. Nutrients and oxygen are introduced through injection wells and circulated through the contaminated zone by pumping one or more producing wells.
The limiting factor in remediation technology is getting the contaminated subsurface material to the treatment unit or units, or in the case of in situ processes, getting the treatment process to the contaminated material. The key to successful remediation is a thorough understanding of the hydrogeologic and geochemical characteristics of the contaminated area.     

The Application of In Situ Air Sparging as an Innovative Soils and Ground Water Remediation Technology

Vapor extraction (soil venting) has been demonstrated to be a successful and cost-effective remediation technology for removing VOCs from the vadose (unsaturated) zone. However, in many cases, seasonal water table fluctuations, drawdown associated with pump-and-treat remediation techniques, and spills involving dense, non-aqueous phase liquids (DNAPLS) create contaminated soil below the water table. Vapor extraction alone is not considered to be an optimal remediation technology to address this type of contamination.
An innovative approach to saturated zone remediation is the use of sparging (injection) wells to inject a hydrocarbon-free gaseous medium (typically air) into the saturated zone below the areas of contamination. The contaminants dissolved in the ground water and sorbed onto soil particles partition into the advective air phase, effectively simulating an in situ air-stripping system. The stripped contaminants are transported in the gas phase to the vadose zone, within the radius of influence of a vapor extraction and vapor treatment system.
In situ air sparging is a complex multifluid phase process, which has been applied successfully in Europe since the mid-1980s. To date, site-specific pilot tests have been used to design air-sparging systems. Research is currently underway to develop better engineering design methodologies for the process. Major design parameters to be considered include contaminant type, gas injection pressures and flow rates, site geology, bubble size, injection interval (areal and vertical) and the equipment specifications. Correct design and operation of this technology has been demonstrated to achieve ground water cleanup of VOC contamination to low part-per-billion levels.     

Measurement of Carbon Dioxide in Soil Gases for Indication of Subsurface Hydrocarbon Contamination

A preliminary field evaluation of a new application of soil-gas measurement for delineation of subsurface organic contamination is described. The method measures carbon dioxide concentrations in soil gases and is based on the hypothesis that carbon dioxide concentrations from subsurface oxidation of organic compounds will be porportional to the extent of organic contamination. A correlation coefficient (r) of 0.81 (n=6) was observed between ground water dissolved organic carbon ground water concentrations and carbon dioxide concentrations in the overlying soil gases at one site. Soil-gas carbon dioxide concentrations measured ranged from 0.09 percent to 0.45 percent.     

Polymer-Enhanced DNAPL Flushing from Low-Permeability Media: An Experimental Study

Remediation of dense nonaqueous phase liquids (DNAPLs) is recognized as one of the most difficult problems associated with ground water pollution. The pump-and-treat technique, usually consisting of a continuous operation of extraction-injection wells, is widely used for ground water remediation. In a stratified or otherwise heterogeneous aquifer, however, this technique suffers from tailing and rebound problems, which limit its cleanup efficiency and result in higher operation costs. The tailing and rebound is usually due to slow diffusion of contaminants out of lower- permeability heterogeneities into the flow regime of the higher-permeability zone. In this study, we conduct bench-scale experiments to investigate a novel polymer system and injection method to improve the pump-and-treat technique for DNAPL trapped in a layer of porous media that has a relatively low permeability compared to the surrounding media. This technique might be useful, for example, to remove DNAPL from these low-permeability zones after removal of DNAPL from the higher-permeability zones by a more traditional remediation method. The polymer system consists of a mixture of anionic and cationic polyacrylamides in solution and the injection method is based on flow-induced polymer adsorption, called bridging adsorption. The study includes single and parallel-column experiments. The measured polymer penetration depths were compared with values predicted from a numerical simulation, which was developed previously by the authors of this paper. The experiments and simulations show that the polymer injection leads to a modification of the permeability contrast that favors a more efficient pump-and-treat process. These results suggest that additional research to upscale the technology to pilot scales is warranted.     

An Overview of In Situ Air Sparging

In situ air sparging (IAS) is becoming a widely used technology for remediating sites contaminated by volatile organic materials such as petroleum hydrocarbons. Published data indicate that the injection of air into subsurface water saturated areas coupled with soil vapor extraction (SVE) can increase removal rates in comparison to SVE alone for cases where hydrocarbons are distributed within the water saturated zone. However, the technology is still in its infancy and has not been subject to adequate research, nor have adequate monitoring methods been employed or even developed. Consequently, most IAS applications are designed, operated, and monitored based upon the experience of the individual practitioner.
The use of in situ air sparging poses risks not generally associated with most practiced remedial technologies: air injection can enhance the undesirable off-site migration of vapors and ground water contamination plumes. Migration of previously immobile liquid hydrocarbons can also be induced. Thus, there is an added incentive to fully understand this technology prior to application.
This overview of the current state of the practice of air sparging is a review of available published literature, consultation with practitioners, a range of unpublished data reports, as well as theoretical considerations. Potential strengths and weaknesses of the technology are discussed and recommendations for future investigations are given.     

Funnel-and-Gate Performance in a Moderately Heterogeneous Flow Domain

The funnel-and-gate ground water remediation technology (Starr and Cherry 1994) has received increased attention and application as an in situ alternative to the typical pump-and-treat system. Understanding the effects of heterogeneity on system performance can mean the difference between a successful remediation project and one that fails to meet its cleanup goals.
In an attempt to characterize and quantify the effects of heterogeneity on funnel-and-gate system performance, a numerical modeling study of 15 simulated heterogeneous flow domains was conducted. Each realization was tested to determine if the predicted capture width met the capture width expected for a homogeneous flow domain with the same hulk properties. This study revealed that the capture width of the funnel-and-gate system varied significantly with the level of heterogeneity of the aquifer.
Two possible remedies were investigated for bringing systems with less than acceptable capture widths to acceptable levels of performance. First, it was determined that enlarging the funnel and gate via a factor of safety applied to the design capture width could compensate for the capture width variation in the heterogeneous flow domains. In addition, it was shown that the use of a pumping well downstream of the funnel and gate could compensate for the effects of aquifer heterogeneity on the funnel-and-gate capture width. However, if a pumping well is placed downstream of the funnel and gate to control the hydraulic gradient through the gate, consideration should be given to the gate residence time in relation to the geochemistry of the contaminant removal or destruction process in the gate.     

Integrated geophysical and chemical study of saline water intrusion

Surface geophysical surveys provide an effective way to image the subsurface and the ground water zone without a large number of observation wells. DC resistivity sounding generally identifies the subsurface formations-the aquifer zone as well as the formations saturated with saline/brackish water. However, the method has serious ambiguities in distinguishing the geological formations of similar resistivities such as saline sand and saline clay, or water quality such as fresh or saline, in a low resistivity formation. In order to minimize the ambiguity and ascertain the efficacy of data integration techniques in ground water and saline contamination studies, a combined geophysical survey and periodic chemical analysis of ground water were carried out employing DC resistivity profiling, resistivity sounding, and shallow seismic refraction methods. By constraining resistivity interpretation with inputs from seismic refraction and chemical analysis, the data integration study proved to be a powerful method for identification of the subsurface formations, ground water zones, the subsurface saline/brackish water zones, and the probable mode and cause of saline water intrusion in an inland aquifer. A case study presented here illustrates these principles. Resistivity sounding alone had earlier failed to identify the different formations in the saline environment. Data integration and resistivity interpretation constrained by water quality analysis led to a new concept of minimum resistivity for ground water-bearing zones, which is the optimum value of resistivity of a subsurface formation in an area below which ground water contained in it is saline/brackish and unsuitable for drinking.     

The Role of Bioattenuation in the Management of Aromatic Hydrocarbon Plumes in Aquifers

Ground water scientists have made significant advances in understanding the soil interactions, hydrogeology, fate and transport, and subsurface microbiology of aromatic hydrocarbons (BTEX) in aquifer systems. It is now generally recognized that a major factor responsible for the attenuation and mass reduction of BTEX in plumes is the widespread occurrence of hydrocarbon biodegradation by indigenous soil microorganisms in aquifer material. Most well-studied BTEX plumes that develop from the accidental release of gasoline fuels contain low levels of soluble hydrocarbons (< 1 to 5000 ppb) and have been shown to be spatially confined because of natural biotransformation mechanisms. These in situ processes are controlled by source and aquifer characteristics, permeability, sorption, and geochemical properties of the aquifer. Many laboratory subsoil-ground water microcosms and field studies (10 to 20 C) have demonstrated the rapid biodecay (1 to SO percent/day for microcosms and 0.5 to 1.5 percent/day for plumes) of these aromatic compounds under primarily aerobic conditions (i.e., those with sufficient dissolved oxygen). The ability to implement ground water bioremediation will depend upon our understanding of source control and aquifer recharge effects on the spatial distribution of plumes. In addition, estimating the biodegradation of sorbed BTEX, determining limits and potential for in situ biostimulation of soluble plumes, and establishing data requirements for predictive modeling of natural attenuation will be useful for this remediation technology. The use of these tools to manage ground water quality appears to represent the most practical alternative, particularly for low-risk ground water supplies.     

Data-worth analysis for multiobjective optimal design of pump-and-treat remediation systems

The design and the management of pump-and-treat (PAT) remediation systems for contaminated aquifers under uncertain hydrogeological settings and parameters often involve decisions that trade off cost optimality against reliability. Both design objectives can be improved by planning site characterization programs that reduce subsurface parameter uncertainty. However, the cost for subsurface investigation often weighs heavily upon the budget of the remedial action and must thus be taken into account in the trade-off analysis. In this paper, we develop a stochastic data-worth framework with the purpose of estimating the economic opportunity of subsurface investigation programs. Since the spatial distribution of hydraulic conductivity is most often the major source of uncertainty, we focus on the direct sampling of hydraulic conductivity at prescribed locations of the aquifer. The data worth of hydraulic conductivity measurements is estimated from the reduction of the overall management cost ensuing from the reduction in parameter uncertainty obtained from sampling. The overall cost is estimated as the expected value of the cost of installing and operating the PAT system plus penalties incurred due to violations of cleanup goals and constraints. The crucial point of the data-worth framework is represented by the so-called pre-posterior analysis. Here, the tradeoff between decreasing overall costs and increasing site-investigation budgets is assessed to determine a management strategy proposed on the basis of the information available at the start of remediation. The goal of the pre-posterior analysis is to indicate whether the proposed management strategy should be implemented as is, or re-designed on the basis of additional data collected with a particular site-investigation program. The study indicates that the value of information is ultimately related to the estimates of cleanup target violations and decision makers’ degree of risk-aversion.     

In Situ Remediation of Jet A in Soil and Ground Water by High Vacuum, Dual Phase Extraction

This report summarizes the initial results of subsurface remediation at Terminal 1, Kenneth International Airport, to remediate soil and ground water contaminated with Jet A fuel. The project was driven and constrained In the const ruction schedule of a major new terminal at the facility. The remediation system used a combination of ground water pumping, air injection, and soil vapor extraction. In the first five months of operation, the combined processes of dewatering, volatilization, and biodegradation removed a total of 36,689 pounds of total volatile and semivolatile organic jet fuel hydrocarbons from subsurface soil and ground water. The. results of this case study have shown that 62 percent of the removal resulted from biodegradation, 21 percent occurred as a result of liquid removal, and 11 percent resulted from the extraction of volatile organic compounds (VOC's).     

Static and push-pull methods using radon-222 to characterize dense nonaqueous phase liquid saturations

Naturally occurring radon in ground water can potentially be used as an in situ partitioning tracer to characterize dense nonaqueous phase liquid (DNAPL) saturations. The static method involves comparing radon concentrations in water samples from DNAPL-contaminated and noncontaminated portions of an aquifer, while the push-pull method involves the injection (push) and extraction (pull) of a radon-free test solution from a single well. In the presence of DNAPL, radon concentrations during the pull phase are retarded, with retardation manifested in greater dispersion of radon concentrations relative to a conservative tracer. The utility of these methods was investigated in the laboratory using a physical aquifer model (PAM). Static and push-pull tests were performed before and after contamination of the PAM sediment pack with trichloroethene (TCE), and after alcohol cosolvent flushing and pump-and-treat remediation. Numerical simulations were used to estimate the retardation factor for radon in push-pull tests. Radon partitioning was observed in static and push-pull tests conducted after TCE contamination. Calculated TCE saturations ranged up to 1.4% (static test) and 14.1% (push-pull test). Post-remediation tests showed decreases in TCE saturations. The results show that radon is sensitive to changes in DNAPL saturation in space and time. However, the methods are sensitive to DNAPL saturation heterogeneity, test location, sample size, and test design. The influence of these factors on test results, as well as the apparent overestimation of the retardation factor in push-pull tests, warrant further investigation.     

DNAPL Flow Behavior in a Contaminated Aquifer: Evaluation of Field Data

A pool of dense nonaqueous phase liquid (DNAPI.) containing TCE and other chlorinated solvents has been removed from the subsurface at Hill Air Force Base, Uthah. as part of an interim remedial action. The removal of the DNAPI. pool means that future off-site migration of dissolved contaminants in the ground water is minimized, and costs for final remedial actions are reduced. A pump-and-treat system recovered more than 23.000) gallons of DNAPI. and one million gallons of contaminated ground water from the aquifer. The efficiency of this remedial action was evaluated on the basis of extensive field and laboratory data. The behavior of DNAPI. flow in the aquifer sands was characterized by collecting core samples from two borings in the DNAPL pool and measuring relative permeabilities and DMAPI. saturation. Core Hooding results show that approximately one-third of the DNAPI. originally in the pool is not recovered by water displacement, but remains as a residual saturation held in place by capillary pressure. However, subsequent Hooding with two pore volumes of surfactant solution reduced the residual DNAPI. saturation in the sand by one order of magnitude. Analytical and numerical models for the DNAPI flow behavior at the site were developed. This is the first time that such models have been developed and applied to an actual DNAPI. pumping lest conducted in the field. Because measured permeabilities and residual saturations were used lo calibrate the models. the model predictions could be used lo provide valuable insights into the controlling mechanisms for DNAPL recovery. The data collection and modeling procedures outlined in this paper can be used lo enhance the efficiency and minimize the cost 10 clean up this and other DNAPI.-contaminated sites.     

Demonstration of a Microbiologically Enhanced Vertical Ground Water Circulation Well Technology at a Superfund Site

A full-scale ground water circulation well (GCW) system was installed and operated to demonstrate in situ remediation of soil and ground water impacted with a mixture of chlorinated and nonchlorinated organic compounds at a Superfund site in upstate New York. System performance and applicability under site-specific conditions were evaluated based on the system's ability to meet the New York State Department of Environmental Conservation (NYSDEC) cleanup goals for target compounds in ground water and soil. Contaminants from the unsaturated zone were mobilized (volatilized) by one-way vacuum extraction, and treated via enhanced biodegradation (bioventing). In the saturated zone, contaminants were mobilized by soil flushing (solubilized) and treated by a combination of air stripping and biodegradation. An in situ aqueous phase bioreactor, and an ex situ gas phase bioreactor, were integrated into the system to enhance treatment via bioremediation. After 15 months of operation, the mass of target contaminants in soil and ground water combined had been reduced by 75%. Removal by biological mechanisms ranged from 35% to 56% of the total observed mass reduction. The in situ and the ex situ bioreactors mineralized 79% and 76%, respectively, of their target biodegradable contaminant loads. Results indicate that some mass reduction in target contaminants may have been from aerobic and aerobic processes within the circulation cell. Nonchlorinated compounds were relatively easy to mobilize (volatilize, solubilize, and/or transport) and treat when compared to chlorinated compounds. The data collected during the 15-month study indicate that remediation could be accomplished at the Sweden-3 Chapman site using the technology tested.     

The Application of a Statistical Trend Analysis Model to Ground Water Monitoring Data from Solid Waste Landfills

A statistical trend methodology is used to compare ground water quality between eight landfill sites in western Michigan as a case study. Monitoring data were collected over a 15-year period on 36 parameters at an upgradient and downgradient well selected at each of the eight sites. This yielded a total of 576 monitoring data sets available for analysis. New trend and contamination indices are introduced that are used to compare ground water contamination between these eight sites. These indices are used to assess each landfill's relative potential for environmental harm.
Many questions remain unanswered, but what is demonstrated here is that this type of methodology has the potential to be used to assess trends of ground water chemistry concentrations at landfill sues in a region. A specific purpose of such an assessment could be to provide a quantified basis for the prioritization of funds allocated for cleanup of contaminated landfill sites. Having a technical capability to reduce large amounts of ground water monitoring data to appropriate summaries, which then can be used to assess environmental contamination between several sites, could also have important economic and health implications in other settings. Hopefully this paper will encourage further development of such technologies for these purposes.     

Modeling a Ground Water Circulation Well Alternative

Ground water circulation wells (GCWs) provide an appealing alternative to typical pump-and-treat ground water remediation systems because of the inherent resource-conservative nature of the GCW systems. GCW performance prediction is challenging because the consideration of extraction and recharge in a single well is unusual for most practitioners, the technology is relatively new, and a meaningful body of literature has not been published. A three-part evaluation process using state-of-the-practice numerical ground water flow and mass transport models was developed for application during GCW pilot studies at the former Nebraska Ordnance Plant site. A small-scale ground water flow model was developed during the pilot study planning process to predict the system performance and to locate performance-measuring monitoring wells. Key predictions included the capture zone predicted to develop upgradient of the GCW, the downgradierit GCW recharge zone, and the circulation zone centered on the GCW. The flow model was subsequently verified using ground water elevation data and contaminant concentration data collected during pilot study operation. Aquifer parameters were reestimated as a result of the verification process. Those parameter values were used as input to a larger scale model, which was used to develop a remedial alternative consisting of multiple GCW systems.     

Cryogenic Core Collection and Preservation of Subsurface Samples for Biomolecular Analysis

A cryogenic coring system for the collection and preservation of biomolecules in unconsolidated subsurface solid samples is presented here. The sampler is based on existing direct‐push coring technology, with the addition of a cryogenic step to freeze the sample in situ. Once brought to the surface, the frozen cores can be packed in dry ice and shipped to the laboratory for further processing and analysis. The approach prevents redistribution of fluids during sample recovery and shipping, and because the cores are frozen in situ there is little loss of solid material during retrieval to ground surface. To evaluate the performance of the approach, DNA analyses of samples collected by cryogenic coring in a very large physical model are compared with results from water samples and horizontal core samples taken in close proximity. The data indicate that the vertical distribution of DNA within the cryogenic core can be measured at the centimeter scale, providing unprecedented characterization of subsurface biogeochemical interfaces.     

Ground Water Remediation Using an Extraction, Treatment, and Recharge System

Ground water remediation of volatile organic compound (VOC) contamination at a site in Michigan was initiated as a result of a consent agreement between the Michigan Department of Natural Resources (MDNR) and the responsible party. Under the direction of the MDNR, the responsible party conducted a remedial investigation/feasibility study using federal guidelines to define the extent of contamination at the site and to select a response action for site remediation. The selected alternative included a combination of ground water extraction, treatment, and recharge, and soil flushing. The extraction system withdraws ground water from various depths in heavily contaminated areas. The ground water is treated using an air stripper. A spray distribution system spreads effluent from the stripper over a recharge basin constructed over the most contaminated areas. Additional contaminant removal is achieved by volatilization from the spray and percolation through the gravel bed. Recharge water moves downward through the contaminated soils, thus flushing residual soil contaminants. The initial operating data demonstrated that the system can effectively remove trichloroethylene (TCE) from ground water (approximately 95 percent overall removal efficiency). The annualized capital and operation and maintenance (O & M) costs of the remedial action were estimated for several operating periods (15, 20, and 30 years).     

Pump-and-treat optimization using analytic element method flow models

Plume containment using pump-and-treat (PAT) technology continues to be a popular remediation technique for sites with extensive groundwater contamination. As such, optimization of PAT systems, where cost is minimized subject to various remediation constraints, is the focus of an important and growing body of research. While previous pump-and-treat optimization (PATO) studies have used discretized (finite element or finite difference) flow models, the present study examines the use of analytic element method (AEM) flow models. In a series of numerical experiments, two PATO problems adapted from the literature are optimized using a multi-algorithmic optimization software package coupled with an AEM flow model. The experiments apply several different optimization algorithms and explore the use of various pump-and-treat cost and constraint formulations. The results demonstrate that AEM models can be used to optimize the number, locations and pumping rates of wells in a pump-and-treat containment system. Furthermore, the results illustrate that a total outflux constraint placed along the plume boundary can be used to enforce plume containment. Such constraints are shown to be efficient and reliable alternatives to conventional particle tracking and gradient control techniques. Finally, the particle swarm optimization (PSO) technique is identified as an effective algorithm for solving pump-and-treat optimization problems. A parallel version of the PSO algorithm is shown to have linear speedup, suggesting that the algorithm is suitable for application to problems that are computationally demanding and involve large numbers of wells.     

In Situ Measurement of Electro-Osmotic Fluxes and Conductivity Using Single Wellbore Tracer Tests

Electro-osmosis (EO), the movement of water through porous media in response to an electric field, offers a means for extracting contaminated ground water from fine-grained sediments, such as clays, that are not easily amenable to conventional pump-and-treat approaches. The EO-induced water flux is proportional to the voltage gradient in a manner analogous to the flux dependence on the hydraulic gradient under Darcy's law. The proportionality constant, the soil electro-osmotic conductivity or k_eo, is most easily measured in soil cores using bench-top tests, where flow is one-dimensional and interfering effects attributable to Darcy's law can be directly accounted for. In contrast, quantification of EO fluxes and k_eo in the field under deployment conditions can be difficult because electrodes are placed in ground water wells that may be screened across a heterogeneous mixture of lithologies. As a result, EO-induced water fluxes constitute an approximate radial flow system that is superimposed upon a Darcy flow regime through permeable pathways that may or may not be coupled with hydraulic head differences created by the EO-induced water fluxes. A single well comparative tracer test, which indirectly measures EO fluxes by comparing wellbore tracer dilution rates between background and EO-induced water fluxes, may provide a means for routinely quantifying the efficacy of EO systems in such settings. EO fluxes measured in field tests through this technique at a ground water contamination site were used to estimate a mean k_eo value through a semianalytic line source model of the electric field. The resulting estimate agrees well with values reported in the literature and with values obtained with bench-top tests conducted on a soil core collected in the test area.     

The Application of Petroleum Hydrocarbon Fingerprint Characterization in Site Investigation and Remediation

Tremendous resources have been and continue to be spent investigating and remediating petroleum hydrocarbon compounds (PHCs) in soil and ground water. Investigating and planning a remedial strategy for sites affected by PHCs is often a challenging task because of the complex chemical nature of the PHCs. the complex regulatory environment related to PHC cleanup, and the use of analytical methods that provide quantitation but not identification of PHCs. From a technical standpoint, the PHC impacting soil and/or ground water is frequently inadequately characterised, both in identification as well as in is general properties (solubility, toxicity). From a regulatory standpoint, promulgated or recommended total petroleum hydrocarbon (TPH) cleanup levels generally relate to assumed properties of specific unweathered products and are inconsistent among different agencies and regions. This produces a prime situation for unwillingly spending more resources on investigation or remediation than may be necessary, especially when the PHC in the subsurface has different properties from unweathered products such as gasoline or diesel.
Accurately identifying the PHC and its nature, a process known as fingerprint characterization, is critical to the determination of appropriate regulatory goals and design of cost-effective remedial approaches. This paper presents several case studies in which fingerprint characterization made a significant difference in the project outcome. In each instance the nature of the organic material was better understood, the regulatory cleanup levels were negotiated based on the nature of the material, and a remedial approach was implemented that differed significantly from and was generally less costly than what would have been required without fingerprint characterization data.